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1.
Seong Kim Patricia M. Cotts Willi Volksen 《Journal of Polymer Science.Polymer Physics》1992,30(2):177-183
The recent introduction of multiangle light-scattering detectors for size-exclusion chromatography has made possible the measurement of the root mean square radius of gyration (Rg) and molecular weight (M) of polymer fractions eluting from a size-exclusion chromatography column. The characterization of the dimensions of a polymer may be accomplished with only a few milligrams. The dimensions of a polyimide precursor prepared by the condensation of the meta-diethyl ester of pyromellitic dianhydride with para-phenylene diamine have been measured with this technique. The dependence of Rg on M across the distribution is compared with that predicted for a freely rotating chain, and with other similar polymers measured with hydrodynamic techniques. 相似文献
2.
Precise synthesis of a series of poly(4‐n‐alkylstyrene)s and their glass transition temperatures
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Satoru Matsushima Atsushi Takano Yoshiaki Takahashi Yushu Matsushita 《Journal of Polymer Science.Polymer Physics》2017,55(9):757-763
Poly(4‐n‐alkylstyrene)s with six kinds of n‐alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, and octyl groups covering wide molecular weight range from around 5 k to over 100 k were precisely synthesized by living anionic polymerizations. It was confirmed that all the polymers obtained have narrow molecular weight distribution, that is, Mw/Mn is all less than 1.1, by SEC. Tgs of all the polymers were estimated by DSC measurements and it turned out to be clear that their molecular weight dependence was well described by the Fox–Flory equations. Furthermore, it is evident that Tg monotonically decreases as a number of carbon atoms of n‐alkyl group is increased, though Tg values are all 20 K or more higher than those reported previously for the same polymer series. This is because backbone mobility increases by introducing longer n‐alkyl side groups with high mobility, while Tg difference in between this work and the previous one may due to the experimental conditions and also to the molecular weight range adopted. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 757–763 相似文献
3.
Quantification of uncertainties involved in the conformational study of polymers by light scattering
Gel permeation chromatography (GPC) combined with a multi-angle light scattering (MALS) is a very powerful characterization technique because it provides both absolute molecular weight (Mw) and the radius of gyration (Rg) throughout the separated slices obtained by GPC. This combination of Mw and Rg, can be used to obtain information about the conformation of polymer chains in solutions and the branching of molecules. Due to the interesting properties obtained for polymers, it is essential to quantify the effect of different error sources in light scattering measurements as well as in the data treatment that highly affect the accuracy of obtained molar mass and radius of gyration. Usually, the results obtained for Mw and Rg in this analysis are dispersed for determined ranges of retention time and to have both reliable Rg and Mw for calculation, only high confidence data points have to be chosen. This range is arbitrarily chosen by the user for the data observation.In this work a new method of calculation to obtain Rg and Mw by means of GPC–MALS technique has been developed. As a first point, a data analysis procedure was set in order to describe both Rg and Mw vs. retention time and to determine the range where experimental data are confident. Several aspects in the data analysis have been studied. The polynomial fit function, the influence of the concentration of the sample, the reproducibility of the experiments and the conformational scaling law have been investigated by statistic technique in order to quantify the uncertainties involved. 相似文献
4.
David Salas‐de la Cruz Matthew D. Green Yuesheng Ye Yossef A. Elabd Timothy E. Long Karen I. Winey 《Journal of Polymer Science.Polymer Physics》2012,50(5):338-346
The morphology and ionic conductivity of poly(1‐n‐alkyl‐3‐vinylimidazolium)‐based homopolymers polymerized from ionic liquids were investigated as a function of the alkyl chain length and counterion type. In general, X‐ray scattering showed three features: (i) backbone‐to‐backbone, (ii) anion‐to‐anion, and (iii) pendant‐to‐pendant characteristic distances. As the alkyl chain length increases, the backbone‐to‐backbone separation increases. As the size of counterion increases, the anion‐to‐anion scattering peak becomes apparent and its correlation length increases. The X‐ray scattering features shift to lower angles as the temperature increases due to thermal expansion. The ionic conductivity results show that the glass transition temperature (Tg) is a dominant, but not exclusive, parameter in determining ion transport. The Tg‐independent ionic conductivity decreases as the backbone‐to‐backbone spacing increases. Further interpretation of the ionic conductivity using the Vogel–Fulcher–Tammann equation enabled the correlation between polymer morphology and ionic conductivity, which highlights the importance of anion hoping between adjacent polymer backbones. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012 相似文献
5.
Abstract Backbone anisotropy and the structure of the mesophases of a series of side-chain liquid crystal polymers have been studied in the bulk by neutron scattering. The backbone conformation is obtained by small-angle neutron scattering on mixtures of hydrogenous polymers with deuteriated backbones. The components of the radius of gyration parallel, R ⊥ and perpendicular, R ∥ to the magnetic field are determined as a function of temperature for both the nematic phase and the smectic phase. It is shown that the polymer backbone is deformed in both phases. When the polymer exhibits only a nematic phase, it adopts a prolate conformation, where the average backbone direction is more or less parallel to the aligned mesogenic groups. Upon transition from the smectic phase to a nematic phase, the backbone in the nematic phase assumes a slightly oblate shape. This tendency towards oblate shape is due to the smectic fluctuations which are always present in such nematic phases. The exentricity of the oblate backbone conformation in the smectic phase is always larger than in the nematic phase. This is attributed to a periodic distribution of the backbone between the mesophase layers. Then, the backbone anisotropy depends not only on the smectic structure (SA1, SAd), but also on the temperature dependence of the density of aligned mesogenic groups in the layers. On the other hand, it is shown that the isotopic mixtures are no longer ideal when polymers deuteriated in the mesogenic moieties are mixed with the corresponding hydrogenous polymers. 相似文献
6.
Z. Florjanczyk B. Deopura R. S. Stein O. Vogl 《Journal of polymer science. Part A, Polymer chemistry》1982,20(4):1051-1063
Poly(2,3-dialkylbutanediol-1,4 terephthalates) with the alkyl substituents CH3, C2H5, n-C3H7, iso-C3H7, n-C4H9, and n-C10H21, andn-C16H33 were synthesized from the corresponding 2,3-dialkylbutanediols-1,4 and dimethyl terephthalate or terephthaloyl chloride. The substituents of the butanediol-1,4 portion of the polyterephthalates influence the 13C NMR chemical shifts of the carbon atoms near the branching site, the glass transition (Tg), and the crystallizability. Small alkyl substituents do not change the Tg of the polymers, whereas bulky substituents such as the isopropyl group increase the Tg and long normal alkyl groups as substituents decrease the Tg of the polymers. Crystallinity in these polyterephthalates was found only with CH3 and C16H33 as the 2,3-dialkyl substituents in the butanediol-1,4 portion of the polyester. This crystallinity of polyterephthalate of 2,3-di-C16H33 substituted butanediol-1,4 could be assigned to side-chain crystallization of the paraffinic groups. 相似文献
7.
George R. Whittell Joe B. Gilroy Isabelle Grillo Ian Manners Robert M. Richardson 《Journal of polymer science. Part A, Polymer chemistry》2013,51(19):4011-4020
A series of monodisperse (Mw/Mn < 1.1) poly(ferrocenyldimethylsilane)s was prepared with number‐averaged degrees of polymerization, 〈z〉n, of 9, 33, 206, and 506 ( 2 – 5 , respectively), as determined by gel permeation chromatography (GPC). The polymers were studied by small‐angle neutron scattering (SANS) in solution with the aim of obtaining the radius of gyration, Rg, the weight‐averaged molecular weight, Mw, and the polydispersity index, Mw/Mn. Data were collected over the range 0.008 < Q/Å?1 < 0.5 and for a series of concentrations (weight fraction, w = 0.0063, 0.0125, 0.025, and 0.05). The scattered intensity, I(Q), was fitted to a model based on a Schultz–Zimm distribution of isolated chains with excluded volume. A comparison of the molecular weight and size data determined by GPC and SANS indicated an acceptable agreement between the values for Rg, Mw and Mw/Mn. The results of this study demonstrate the potential utility of SANS to fully characterize metallopolymers, and other polymer systems where traditional methods cannot be applied. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4011–4020 相似文献
8.
Kamil Kotwica Anastasia S. Kostyuchenko Dr. Przemyslaw Data Dr. Tomasz Marszalek Lukasz Skorka Dr. Tomasz Jaroch Sylwia Kacka Prof. Malgorzata Zagorska Prof. Robert Nowakowski Prof. Andrew P. Monkman Prof. Alexander S. Fisyuk Prof. Wojciech Pisula Prof. Adam Pron 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(33):11795-11806
Star‐shaped conjugated molecules, consisting of a benzene central unit symmetrically trisubstituted with either oxa‐ or thiadiazole bithiophene groups, were synthesized as promising molecules and building blocks for application in (opto)electronics and electrochromic devices. Their optical (Eg(opt)) as well as electrochemical (Eg(electro)) band gaps depended on the type of the side arm and the number of solubilizing alkyl substituents. Oxadiazole derivatives showed Eg(opt) slightly below 3 eV and by 0.2 eV larger than those determined for thiadiazole‐based compounds. The presence of alkyl substituents in the arms additionally lowered the band gap. The obtained compounds were efficient electroluminophores in guest/host‐type light‐emitting diodes. They also showed a strong tendency to self‐organize in monolayers deposited on graphite, as evidenced by scanning tunneling microscopy. The structural studies by X‐ray scattering revealed the formation of supramolecular columnar stacks in which the molecules were organized. Differences in macroscopic alignment in the specimen indicated variations in the self‐assembly mechanism between the molecules. The compounds as trifunctional monomers were electrochemically polymerized to yield the corresponding polymer network. As shown by UV/Vis‐NIR spectroelectrochemical studies, these networks exhibited reversible electrochromic behavior both in the oxidation and in the reduction modes. 相似文献
9.
K. Levon E. Chu K.-S. Ho T. K. Kwei J. Mao W.-Y. Zheng J. Laakso 《Journal of Polymer Science.Polymer Physics》1995,33(4):537-545
The mixing of electrically conducting polymers in the undoped state with flexible polymers has been limited due to the stiffness of the delocalized coplanar backbone. The substitution with alkyl side chains has resulted in the distortion of the aromatic rings in the backbone with an increase of the flexibility. The alkyl substituents also prevent the thiophene back-bones from packing together, thus making blending with other polymers promising. We have investigated the phase behavior of poly(3-octylthiophene) (P3OT) with a flexible polymer, poly(ethylene-co-vinylacetate) (vinylacetate composition 20%, EVA20), and defined a miscibility window based on melting point data, on cloud point measurements, and on analysis by optical microscopy. The miscible region has been studied by UV-VIS and CPMAS NMR spectroscopies. A UV absorption in the visible region originates from a π-π * transition in the delocalized structure of P3OT, and a change in the length of the conjugated segment in the backbone results in a shift of this absorption. A gradual solvatochromatic shift of P3OT in the solid state with dilution was observed in the miscible region. T1 relaxation times for the methylene carbons in solid state show a gradual change in the relaxation process as a function of composition. © 1995 John Wiley & Sons, Inc. 相似文献
10.
The small-angle neutron scattering (SANS) method for measuring the self-diffusion coefficient D has been analyzed for effects of polydispersity in degree of polymerization for the case of linear polymers diffusing by reptation. Polydispersities corresponding to Mw/Mn = 1.0?10 were considered. It is shown that in all cases a meaningful effective diffusion coefficient De can be obtained from the short time recovery of the SANS intensity. This quantity De ≤ 1.3 D(Mw), where D(Mw) is the diffusion coefficient of a monodisperse polymer having molecular weight M = Mw. The method relies on SANS intensities extrapolated to zero scattering angle; realistic extrapolation is shown to give rise to quite acceptable errors on the order of 0.05 De. 相似文献
11.
Edoardo De Luca Randal W. Richards 《Journal of Polymer Science.Polymer Physics》2003,41(12):1339-1351
A hyperbranched polyester was fractionated by precipitation to produce 10 fractions with molecular weights between 20 × 103 and 520 × 103 g mol?1. Each of these fractions was examined by size exclusion chromatography, dilute‐solution viscometry, intensity, and quasi‐elastic light scattering in chloroform solution at 298 K. High‐resolution solution‐state 13C NMR was used to determine the degree of branching; for all fractions this factor was 0.5 ± 0.1. Viscometric contraction factors, g′, decreased with increasing molecular weight, and the relation of this parameter to the configurational contraction factor, g, calculated from a theoretical relation suggested a very strong dependence on the universal viscosity constant, Φ, on the contraction factor. A modified Stockmayer–Fixman plot was used to determine the value of (〈r2〉o/Mw)1/2, which was much larger than the value for the analogous linear polymer. The scaling relations of the various characteristic radii (Rg, Rh, RT, and Rη) with molecular weight all had exponents less than 0.5 that agreed with the theoretical predictions for hyperbranched polymers. The exponent for Rg was interpreted as fractal dimension and had a value of 2.38 ± 0.25, a value that is of the same order as that anticipated by theory for branched polymers in theta conditions and certainly not approaching the value of 3 that would be associated with the spherical morphology and uniform segment density distribution of dendrimers. Second virial coefficients from light scattering are positive, but the variation of the interpenetration function, ψ, with molecular weight and the friction coefficient, ko, obtained from the concentration dependence of the diffusion coefficient suggests that chloroform is not a particularly good solvent for the hyperbranched polyester and that the molecules are soft and penetrable with little spherical nature. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1339–1351, 2003 相似文献
12.
The tube diameter in the reptation model is the distance between a given chain segment and its nearest segment in adjacent chains. This dimention is thus related to the cross-sectional area of polymer chains and the nearest approach among chains, without effects of thermal fluctuation and steric repulsion. Prior calculated tube diameters are much larger, about 5 times, than the actual chain cross-sectional areas. This is ascribed to the local freedom required for mutual rearrangement among neighboring chain segments. This tube diameter concept seems to us to infer a relationship to the corresponding entanglement spacing. Indeed, we report here that the critical molecular weight, Mc, for the onset of entanglements is found to be Mc = 28 A/(〈R2〉0/M), where A is the chain cross-sectional area and 〈R2〉0 the mean-square end-to-end distance of a freely jointed chain of molecular weight M. The new, computed relationship between the critical number of backbone atoms for entanglement and the chain cross-sectional area of polymers, Nc = A0,44, is concordant with the cross-sectional area of polymer chains being the parameter controlling the critical entanglement number of backbone atoms of flexible polymers. 相似文献
13.
Demonstration of isospecific free radical polymerization of acrylate controlled by conformation and chirality of monomer
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Hitoshi Tanaka Yoshitaka Matsubara Katsuhiko Kusunoki Naoki Saito Tatsuya Kibayashi 《Journal of polymer science. Part A, Polymer chemistry》2015,53(17):2007-2016
Radical polymerization of lactic acid‐based chiral and achiral methylene dioxolanones, a model for conformationally s‐cis locked acrylate, was carried out with AIBN to demonstrate an isospecific free radical polymerization controlled by chirality and conformation of monomer. Polymerization of the dioxolanones proceeded smoothly without ring opening to give a polymer with moderate molecular weight and 100% of maximum isotacticity. ESR spectrum indicated a twisted conformation of the growing poly(methylene dioxolanone) radical in contrast to an acyclic analogous radical, suggesting a restriction of the free rotation around main chain Cα? Cβ bond of the growing radical center. Chirality as well as the polarity and bulkiness of monomer affected the polymer tacticity, and chiral alkyl substituent would afford a high isotactic polymer, in which higher the enantiomeric excess of the monomer was, higher the isotacticity of the polymer was. While, achiral or polar substituents including dibenzyl and trichloromethyl groups would afford an atactic polymer. In addition, glass transition temperature (Tg) of the resulting polymers was significantly high, ranging from 172.2 to 229.8 °C, and even for an isotactic polymer Tg was as high as 206.8 °C. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2007–2016 相似文献
14.
Gwang‐Su Byun Sang Youl Kim Iwhan Cho 《Journal of polymer science. Part A, Polymer chemistry》2006,44(3):1263-1270
(?)‐(1S,2R)‐Norbornene‐2‐carboxylic acid alkyl esters (alkyl = Me, Bz, L ‐menthyl, or D ‐menthyl) were successfully prepared by the Diels–Alder reaction of cyclopentadiene with (R)‐(?)‐pantolactone‐O‐yl acrylate followed by epimerization and column chromatography. The enantiomeric excess was 99.9%. These monomers were polymerized by Pd(II)‐based catalysts, and high yields of the polymers were obtained. The methyl ester gave an optically active polymer of high optical rotation (monomer [α]D = ?24.7, polymer [α]D = ?98.5). This high rotation value of the polymer was attributed to the isotactic chain regulation of the polymer. This high rotation was not observed with methyl esters prepared by the transesterification of menthyl esters. The stereoregular polymer exhibited notable resonance peaks at 39 ppm in 13C NMR spectra. No crystallinity was observed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1263–1270, 2006 相似文献
15.
A number of polymers belonging to poly(olefin oxide) and poly(olefin sulfide) series have been prepared and their glass transformation temperatures determined by dilatometry and differential thermal analysis. In the poly(olefin oxide) series, the Tg remained practically unchanged as the length of the pendent alkyl group was increased from methyl to n-hexyl. However, a 20°C decrease in Tg was observed when the pendent group was changed from ethoxymethyl to n-hexoxymethyl. In the poly-(olefin sulfide) series, the Tg value decreased as the pendent alkyl group changes from methyl to ethyl. Replacement of ether oxygen in the polymer main chain by sulfide sulfur increased the Tg value. In some polymers, first-order transitions were observed, but their significance has not been assessed. 相似文献
16.
Rui Pan Wei Zhao Tao Zhou Aiming Zhang 《Journal of Polymer Science.Polymer Physics》2010,48(5):595-599
Three polyetherimides (PEIs) with the same backbone of Ultem 100 but different lengths of the alkyl side chains were simulated by using molecular dynamics and molecular mechanics techniques to investigate the effect of side chain length on their properties and physical mechanism behind. Simulation results, which are consistent to the experimental data, show that PEI‐5 with four methylene units in each alkyl side chain has higher Tg (glass transition temperature) and higher tensile strength, but lower tensile elongation at break than those of PEI‐6 with five and PEI‐8 with seven methylene units in each alkyl side chain. However, unlike the traditional phenomena, conformational analysis provides that PEI‐5 with the highest Tg gives the highest flexibility to the polymer chain, whereas PEI‐8 with the lowest Tg imparts the lowest flexibility resulting from attachment of longer alkyl side chain increase the rigidity of backbone. From the calculated ratio of the accessible volume to the total volume for each system, the highest ratio of PEI‐8 indicates that long alkyl side chains generate more free volume than short side chains, acting as an internal plasticizer in bulk structure. It is the internal plasticizing effect that is predominantly responsible for the abnormal properties, instead of the rigidity from side chains. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 595–599, 2010 相似文献
17.
The Mechanical Strength of a Mechanical Bond: Sonochemical Polymer Mechanochemistry of Poly(catenane) Copolymers
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Bobin Lee Zhenbin Niu Prof. Dr. Stephen L. Craig 《Angewandte Chemie (International ed. in English)》2016,55(42):13086-13089
Topological molecular connections and structures, including physical entanglements in polymer networks, knots along polymer chains, and rotaxanes in sliding ring gels, have important consequences for the physical properties of polymeric materials. Often these topologies contribute through their ability to bear mechanical stress, but experimental measures of their relative mechanical strength are rare. Here, we use sonochemical polymer mechanochemistry to assess the relative mechanical strength of a multicatenane copolymer relative to copolymers of cyclic and linear analogs. The relative mechanical strengths are obtained by comparing the limiting molecular weights (Mlim) and contour lengths (Llim) of the polymers under pulsed ultrasound of their dilute solutions. The values of Mlim and Llim, and thus the inferred mechanical strengths of the polymers, are effectively identical. The mechanical bonds of the catenanes are therefore as strong, or stronger, mechanically as the covalent bonds along the polymer backbone. 相似文献
18.
A new class of linear unsaturated polyphosphate esters based on divanillylidene cyclohexanone possessing liquid crystalline‐cum‐photocrosslinkable properties have been synthesized from 2,6‐bis[n‐hydroxyalkyloxy(vanillylidene)]cyclohexanone [n = 6,8,10] with various alkyl/aryl phosphorodichloridates in chloroform at ambient temperature. The resultant polymers were characterized by intrinsic viscosity, FT‐IR, 1H, 13C, and 31P‐NMR spectroscopy. All the polymers showed anisotropic behavior under hot stage optical polarized microscope (HOPM). The liquid crystalline textures of the polymers became more transparent with increasing spacer length. The thermal behavior of the polymers was studied by thermogravimetric analysis and differential scanning calorimetry. The Tg, Tm, and Ti of the polymers decreased with increasing flexible methylene chain. The photocrosslinking property of the polymer was investigated by UV light/UV spectroscopy; the crosslinking proceeds via 2π‐2π cycloaddition reactions of the divanillylidene exocyclic double bond of the polymer backbone. The pendant alkyloxy containing polymers show faster crosslinking than the pendant phenyloxy containing polymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5215–5226, 2004 相似文献
19.
Ravi Aggarwal Durairaj Baskaran 《Journal of polymer science. Part A, Polymer chemistry》2018,56(19):2225-2237
The supported aqueous-phase catalysis (SAPC) using hydrated interface has been used to synthesize branched polymers (star and graft) of benzyl methacrylate (BnMA) via atom-transfer radical polymerization (ATRP) in the presence of Na-clay supported catalyst in anisole at ambient temperature. The propagation of star poly(BnMA)s using diPENDTA-Br6, as hexa-functional initiator is confined at the hydrated interface between the support and the liquid medium as evident from the obtained polymers that are catalyst contamination-free, and exhibited moderately narrow molecular weight distributions (Mw/Mn ≤ 1.33). The hexa-functionality of synthesized stars is verified by 1H NMR, the measurement of their intrinsic viscosity ([η]), and radius of gyration (Rg). The polymerization was also recycled up to 5 times to produce star PBnMAs with high initiator efficiency. The star polymers prepared using hydrated Na-clay supported is compared with star prepared using covalent silica supported catalyst system. The star polymer obtained from covalently supported catalyst gave broad Mw/Mn and poor initiator efficiency. The polystyrene-graft-PBnMA (PS-g-PBnMA) copolymer is also prepared using hydrated Na-clay supported catalyst system in anisole at ambient temperature. The graft-copolymer had narrow Mw/Mn and was confirmed using 1H NMR and atomic force microscopy. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2225–2237 相似文献
20.
Alan William Hall David Lacey Peter Ian Buxton 《Macromolecular rapid communications》1996,17(6):417-425
The technique of photoinitiated free-radical cyclopolymerization has been used to produce a variety of novel side-chain liquid-crystalline (SCLC) polymers in which an alicyclic ring structure is incorporated into a polymer backbone. Most of the SCLC polymers gave glass transition temperatures (Tg) around room temperature and clearing points around 60–70°C. However, the poly(1,5-hexadiene) was the exception to this, exhibiting a Tg value of 14.5°C and a clearing point of 132.5°C. Confirmation of the structure of the alicyclic ring along the polymer backbone is extremely difficult to obtain, but evidence is given in the paper to support the ring structure. 相似文献